Monovalent group 13 diyls are versatile reagents in oxidative addition reactions. We report here [1,4]-cycloaddition reactions of β-diketiminate-substituted diyls LM (M = Al, Ga, In, Tl; L = HC[C(Me)NDipp]
2, Dipp = 2,6-
iPr
2C
6H
3) with
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Monovalent group 13 diyls are versatile reagents in oxidative addition reactions. We report here [1,4]-cycloaddition reactions of β-diketiminate-substituted diyls LM (M = Al, Ga, In, Tl; L = HC[C(Me)NDipp]
2, Dipp = 2,6-
iPr
2C
6H
3) with various 1,2-diketones to give 5-metalla-spiro[4.5]heterodecenes
1,
4–
6, and
8–
10, respectively. In contrast, the reaction of LTl with acenaphthenequinone gave the [2,3]-cycloaddition product
7, with Tl remaining in the +1 oxidation state. Compound
1 also reacted with a second equivalent of butanedione as well as with benzaldehyde in aldol-type addition reactions to the corresponding α,β-hydroxyketones
2 and
3, while a reductive activation of a benzene ring was observed in the reaction of benzil with two equivalents of LAl to give the 1,4-aluminacyclohex-2,4-dien
12. In addition, the reaction of L’BCl
2 (L = HC[C(Me)NC
6F
5]
2) with one equivalent of benzil in the presence of KC
8 gave the corresponding 5-bora-spiro[4.5]heterodecene
13, whereas the hydroboration reaction of butanedione with L’BH
2 (
14), which was obtained from the reaction of L’BCl
2 with L-selectride, failed to give the saturated 5-bora-spiro[4.5]heterodecane.
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